Hydroprocessing technology
Hydroprocessing is a catalytic process that enables targeted catalytic reactions with the
addition of hydrogen. The aim of hydroprocessing is to increase the hydrogen-to-carbon
ratio and to almost completely remove undesirable heteroatoms such as sulfur, nitrogen,
oxygen and some metals. Furthermore, in some cases, hydroprocessing also targets to the
reduction of olefin and the aromatic content of the feedstock. The key reactions involved in
hydroprocessing include hydrodesulphurization (HDS), hydrodenitrogenation (HDN),
hydrodemetallization (HDM), hydrogenation (HYD) and hydrodeoxygenation (HDO). HDS
and HDN enable sulfur and nitrogen removal respectively [100], both of which are
environmentally driven, aiming to mitigate SOX and NOX emissions of fuel combustion.
HDM reactions focus on the removal of the present metals that severely poison the
conversion catalysts during downstream refinery processes. HYD reactions favor the
saturation of feedstocks and the reduction of aromatics, when required, and they are also
a perquisite for further conversion reactions such as hydrocracking. HDO reactions are
necessary for the removal of oxygen compounds, which are not desired in certain refinery
products such as kerosene. HDO reactions are particularly important for bio-based
feedstocks some of which might contain as much as 50 wt% oxygen. For this reason, HDO
reactions are of high importance during the hydroprocessing or co-hydroprocessing of bio-
based feedstocks.
In general, catalytic hydroprocessing is widely employed in all refineries worldwide to
upgrade fossil-based intermediate streams. Each hydroprocessing plant within a refinery
focuses on a single or a combination of the aforementioned reactions depending on the
application, rendering multiple hydroprocessing plants within a single refinery. The
availability and flexibility of the underlying refinery hydroprocessing plants render this
process a suitable candidate for the parallel conversion of bio-based
feedstocks/intermediates within a refinery. Furthermore, in many cases some refinery
streams are of such low quality (e.g., having high polyaromatic and sulfur contents) that
their individual upgrading to fuels is not profitable, such as the light cycle oil (LCO) formed
in an FCC plant which is being co-hydroprocessed with SRGO [42]. In such cases, co-
hydroprocessing with liquid bio-based feedstocks and/or intermediates may better justify
their upgrading, while in some cases even improve the exploitation potential of such low-
quality refinery streams. All the targeted hybrid fuels produced via co-hydroprocessing of
bio-based with petroleum streams can fulfill the high-bio-content-fuels requirements of
the relevant directives of the European Union as described in the introduction section, by
utilizing existing infrastructures.
In general, there are two pathways during biomass hydroprocessing, the first one is
hydrodeoxygenation in which 1 triglyceride molecule consumes 12 hydrogen molecules to
form 3 normal hydrocarbons with an even number of carbon atoms in their
molecules, e.g., n-octadecane (n-C18H38), and the second one is hydrodecarboxylation in
which 1 triglyceride molecule consumes 3 hydrogen molecules to form 3 normal
hydrocarbons with an odd number of carbon atoms in their molecules, e.g., n-
heptadecane (n-C17H36) as they are depicted in Fig. 4 [38]. Typically, the main products for
hydrogenation of triglycerides are hydrocarbons (n-alkanes) and by-products are propane,
water, CO and CO2 [101]. A byproduct is a product with lower economic value than the
main product.